Successes and Failures of Hartree-Fock Theory

TABLE 2.1. SCF Total Energies (liartrees) of CH4, NH3, H2O, anti HE as a Function of Basis Set  

Hartree-Fock theory is a rigorous ab initio theory of electronic structure and has a vast array of successes to its credit. Equilibrium structures of most molecules are calculated almost to experimental accuracy, and reasonably accurate properties (e.g., dipole moments and IR and Raman intensities) can be calculated from HF wave functions. Rela- 

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Surveying the history of the theory of optical lanthanide spectroscopy, we can discern several main features the usefulness of Lie groups, following their introduction by Racah (1949) the relevance of the method of second quantization, as demonstrated by the use of annihilation and creation operators for electrons and the inability of the Hartree-Fock method and its various elaborations to provide accurate values (say to within 1%) of such crucial quantities as the Slater integrals F (4f,4f) and the Sternheimer correction factors R , for a free ion. The success of the formal mathematics is in striking contrast to the failure of the machinery of computation. This turn of events has happened over a period of time when... 

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